Chiral ligand metal complex catalyst system, and its preparation method and use

A metal complex, catalytic system technology, applied in the direction of organic compound/hydride/coordination complex catalyst, catalytic reaction, physical/chemical process catalyst, etc., can solve the narrow application scope and limited application of ligand substrates problem, to achieve the effect of low synthesis cost, wide application range and easy operation

Inactive Publication Date: 2005-02-16
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Recently, monodentate chiral phosphite and phosphoramidite ligands have also been developed successively. Although such ligands are easy to synthesize and stable in structure, their chiral induction ability and ligand substrate The scope of application is relatively narrow, which also limits its application in industry

Method used

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  • Chiral ligand metal complex catalyst system, and its preparation method and use
  • Chiral ligand metal complex catalyst system, and its preparation method and use
  • Chiral ligand metal complex catalyst system, and its preparation method and use

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0044]Add vitriol oil (20ml) in the there-necked flask with mechanical stirring of 1000ml, D-mannitol (100g), benzaldehyde (120ml) and solvent DMF (300ml), after this reaction mixture was stirred at room temperature for 3 days, the reaction The mixture was poured into ice water containing 30 g of potassium carbonate and 500 ml of petroleum ether and stirred vigorously until the ice melted. The solid was filtered and washed with petroleum ether. The solid was extracted twice with 400 ml of boiling chloroform, and the filtered solid was recrystallized from methanol. The product 1 (86 g, 42%) was obtained as a white solid.

[0045] In a 250ml round-bottomed flask, add sodium hydride (12mmol, content 80% sodium hydride dissolved in mineral oil), the compound 1 (10mmol) synthesized in the previous step, solvent DMF (40ml), and the reaction mixture was heated at room temperature After stirring the reaction for 1 hour, iodomethane (10 mmol) was added to continue the reaction at room ...

Embodiment 2

[0051] Under nitrogen protection, 2.0mg (0.005mmol) [Rh(COD) 2 ] BF 4 , with the above-mentioned synthesized chiral ligand ManniPhos (0.010mmol), solvent dichloromethane (1ml) in a 10ml reactor at room temperature, reacted for 10-30 minutes to make a catalyst, and the hydrogenation reaction substrate 2-acetyl Aminocinnamic acid methyl ester (0.5mmol) is transferred in this reactor, after hydrogen displacement 3 times, continue to pass into hydrogen, maintain normal pressure reaction after 30 minutes and stop reaction, filter with short silica gel column, after the filtered gained filtrate is concentrated, use The content and optical purity were determined by GC, and the yield of methyl S-acetamidophenylpropionate was 100% (calculated as methyl 2-acetamidocinnamate), and the enantiomeric excess was 98.0% ee.

Embodiment 3

[0053] Under nitrogen protection, 2.0mg (0.005mmol) [Rh(COD) 2 ] BF 4 , with the chiral ligand ManniPhos (0.010mmol) of above-mentioned synthesis, solvent methylene chloride (1ml) in the reactor of 10ml at room temperature, react 10-30 minute and make catalyst, the hydrogenation reaction substrate dopa The precursor (0.5 mmol) was transferred to the reactor, hydrogen was replaced 3 times, and hydrogen was continuously introduced, and the reaction was terminated after maintaining normal pressure for 30 minutes, filtered through a short silica gel column, and the filtered filtrate was concentrated, and the content was determined by GC. And optical purity measurement, the yield of L-dopa was 100% (based on the precursor of dopa), and the enantiomeric excess was 98.0% ee.

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Abstract

The invention relates to chirality phosphine ligand metal complex catalyse system, which is composed by complex formed by ligand and metal Rh, Ru, Ir, Pt or Pd or ligand and metal precursor in of 1-2 mol ratio. The phosphine ligand is a kind of effective chirality phosphate ligand composed by D-mannitol or L-mannitol after reaction. The catalyst composed by the chirality ligand and rhodium metallic compound in asymmetry hydrogenation reaction can work in room temperature. With a wide applied range, catalyst's activation and stereoselectivity is not influenced from normal pressure to high pressure. Reaction time is 1-24 hours. Mol ratio of ligand and metal rhodium compound is 1:1-2:1. Ratio of reactant and catalyst is 100-10,000.

Description

technical field [0001] The invention relates to a chiral ligand metal complex catalytic system; [0002] The present invention also relates to the preparation method of the above-mentioned catalytic system; [0003] The present invention also relates to the use of the above-mentioned catalytic system in asymmetric hydrogenation reactions. Background technique [0004] Catalytic asymmetric hydrogenation is the core technology in asymmetric synthesis and one of the most effective methods for synthesizing optically pure chiral drugs, pesticides, food additives, and spices, and the design and synthesis of chiral ligands is the key to realizing this core technology factor. At present, many chiral bidentate phosphine ligands have been developed one after another. However, most of the ligands are difficult to synthesize, have poor stability, and are expensive to synthesize and cannot be applied to industrial production. Therefore, they have been successfully applied to industrial...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/18
CPCB01J2231/645B01J2531/0272B01J31/185B01J2231/643B01J2531/0266B01J2531/822
Inventor 郑卓黄汉民陈惠麟罗会礼白长敏
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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